The present invention relates to novel reactive dyes, processes for their preparation and their use for dyeing or printing textile fibre materials.
The practice of dyeing using reactive dyes has recently led to increased requirements regarding the quality of the dyeings and the economics of the dyeing process. Consequently, there continues to be a need for novel reactive dyes which have improved properties, in particular in respect of application.
Reactive dyes which have an adequate substantivity and at the same time a good ease of washing off of the non-fixed portions are now required for dyeing. They should furthermore show a good dyeing yield and have a high reactivity, and, in particular, dyeings with high degrees of fixing should be produced. The known dyes do not meet these requirements in all properties.
The present invention is therefore based on the object of discovering novel, improved reactive dyes for dyeing and printing fibre materials which have the qualities described above to a high degree. The novel dyes should be distinguished, in particular, by high fixing yields and high fibre-dye bond stabilities, and furthermore the portions not fixed on the fibre should be easy to wash off. They should furthermore produce dyeings with good allround properties, for example light and wet fastness properties.
It has been found that the set object can be largely achieved with the novel reactive dyes defined below.
The present invention relates to compounds of the formula 
in which Z is the radical of a diazo component,
R is substituted or unsubstituted C1-C4alkyl,
R1 is hydrogen or substituted or unsubstituted C1-C4alkyl,
X is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl and
D is the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore,
with the provisos that (i) at least one of the radicals D and Z carries a fibre-reactive radical xe2x80x94SO2xe2x80x94Y or xe2x80x94NHCOxe2x80x94Y1, in which
Y is vinyl or a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U,
U is a leaving group,
Y1 is a group xe2x80x94CHX1xe2x80x94CH2X1 or xe2x80x94CX1xe2x95x90CH2 and
X1 is bromine or chlorine,
and that (ii) the radical xe2x80x94NR1xe2x80x94 is not bonded to a phenylene radical substituted by xe2x80x94NH2 if D is the radical of a monoazo or disazo chromophore.
The radical xe2x80x94NRxe2x80x94 can be bonded to the hydroxynaphthalenesulfonic acid radical in the 7-position or, preferably, in the 6-position.
Substituted or unsubstituted C1-C4alkyl R or R1 can be, for example, methyl, ethyl, n- or iso-propyl or n-, sec-, tert- or iso-butyl which are unsubstituted or substituted, for example by hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, C1-C4alkoxycarbonyl or carbamoyl.
R is preferably unsubstituted C1-C4alkyl, particularly preferably methyl or ethyl, and especially preferably methyl.
R1 is preferably hydrogen or C1-C4alkyl which is unsubstituted or substituted by hydroxyl, particularly preferably hydrogen, methyl or ethyl, and especially preferably hydrogen.
X is preferably halogen, for example fluorine, chlorine or bromine, and particularly preferably fluorine or chlorine.
Z is, for example, the radical of an aminobenzene, aminonaphthalene, phenylazoaminobenzene or phenylazoaminonaphthalene, which can be further substituted by substituents customary in dyes.
Suitable substituents on the radical Z are, for example, sulfo; C1-C4alkyl, in particular methyl; hydroxyl; C1-C4alkoxy, in particular methoxy; C1-C4alkoxy which is substituted by hydroxyl, methoxy, ethoxy or sulfato, for example xcex2-hydroxyethoxy, xcex2-sulfatoethoxy or xcex2-methoxyethoxy; halogen, in particular chlorine; C2-C4alkanoylamino, for example acetylamino or propionylamino; ureido; or a fibre-reactive radical of the formula
xe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(2a), 
xe2x80x94CONHxe2x80x94(CH2)nxe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(2b), 
xe2x80x94(O)pxe2x80x94(CH2)mxe2x80x94CONHxe2x80x94(CH2)nxe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(2c), 
xe2x80x94NHxe2x80x94COxe2x80x94Y1xe2x80x83xe2x80x83(2d) 
or 
in which Y and Y1 are each as defined above,
Xxe2x80x2 is independently as defined and preferred above for X,
T is a non-reactive amino radical,
p is the number 0 or 1 and
m and n independently of one another are each an integer from 1 to 6.
In a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U Y, the leaving group U can be, for example, xe2x80x94Cl, xe2x80x94Br, xe2x80x94F, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, OPO3H2, xe2x80x94OCOxe2x80x94C6H5, OSO2xe2x80x94C1-C4alkyl or xe2x80x94OSO2xe2x80x94N(C1-C4alkyl)2. U is preferably a group of the formula xe2x80x94Cl, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OCOxe2x80x94C6H5 or xe2x80x94OPO3H2, in particular xe2x80x94Cl or xe2x80x94OSO3H, and particularly preferably xe2x80x94OSO3H.
Y is preferably vinyl, xcex2-chloroethyl, xcex2-sulfatoethyl, xcex2-thiosulfatoethyl, xcex2-acetoxyethyl, xcex2-phenoxyethyl or xcex2-phosphatoethyl, and particularly preferably xcex2-sulfatoethyl or vinyl.
Y1 is a group xe2x80x94CHX1xe2x80x94CH2X1 or xe2x80x94CX1xe2x95x90CH2, in which X1 is chlorine or, preferably, bromine.
n is preferably the number 2, 3 or 4, particularly preferably the number 2 or 3, and especially preferably the number 2. m is preferably the number 1, 2 or 3, and particularly preferably the number 1 or 2. p is preferably the number 0.
A non-reactive amino radical T can be, for example, amino; Nxe2x80x94C1-C4alkylamino or N,N-di-C1-C4alkylamino, in which the alkyl can in each case be substituted, for example by sulfo, sulfato, hydroxyl, carboxyl or phenyl; cyclohexylamino; phenylamino or naphthylamino, in which the phenyl or naphthyl can in each case be substituted, for example by C1-C4alkyl, C1-C4alkoxy, amino, C2-C4alkanoylamino, carboxyl, sulfo or halogen; N-C1-C4alkyl-N-phenylamino, in which the alkyl and phenyl can optionally be substituted as described above, or morpholino.
Examples of suitable non-reactive amino radicals T are amino, methylamino, ethylamino, xcex2-hydroxyethylamino, N,N-di-xcex2-hydroxyethylamino, xcex2-sulfoethylamino, cyclohexylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, 2,4- or 2,5-disulfophenylamino, 2- or 3-sulfo-4-methoxyphenylamino, 2- or 3-sulfo-4-methylphenylamino, 4-methyl-2,5-disulfophenylamino, o-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 1,5-disulfo-2-naphthylamino, 6,8-disulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, 4,6,8-trisulfo-2-naphthylamino, 1,5,7-trisulfo-2-naphthylamino, 3,6,8-trisulfo-2-naphthylamino, 1,6-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, N-xcex2-sulfoethyl-N-phenylamino, xcex2-hydroxyethyl-N-phenylamino and morpholino.
T is preferably amino, N-mono- or N,N-di-C1-C2-alkylamino, which is unsubstituted or substituted by hydroxyl, sulfo or sulfato, cyclohexylamino, phenylamino or naphthylamino, which are unsubstituted or substituted by methyl, methoxy, carboxyl or sulfo, Nxe2x80x94C1-C2alkyl-N-phenylamino or morpholino and particularly preferably amino, N-mono- or N,N-di-C1-C2alkyl-amino which is unsubstituted or substituted by sulfo, phenylamino which is substituted by 1 to 3 identical radicals from the group consisting of methyl, methoxy and sulfo, or 1- or 2-naphthylamino which carries 1 to 3 sulfo groups.
Examples of preferred radicals Z are:
(a) phenyl which is substituted by one or more identical or different substituents from the group consisting of sulfo, C1-C4alkyl, C1-C4alkoxy and reactive radicals of the formulae (2a), (2b) or (2d) defined above;
(b) 1- or 2-naphthyl which is substituted by sulfo or a reactive radical of the formula (2a) defined above;
(c) a radical of the formula 
in which (R2)0-2 is 0 to 2 identical or different radicals R2 from the group consisting of sulfo; methyl, methoxy, xcex2-hydroxyethoxy, xcex2-sulfatoethoxy, xcex2-methoxyethoxy, acetylamino and ureido and (R3)0-3 is 0 to 3 identical or different radicals from the group consisting of sulfo, methyl and methoxy; and
(d) a radical of the formula 
in which Txe2x80x2 is independently as defined and preferred above for T, Xxe2x80x3 is independently as defined and preferred above for X, and (R4)1-2 is 1 or 2 identical or different radicals R4 from the group consisting of methyl, methoxy, sulfo and reactive radicals of the formulae (2a), (2b) and (2d) defined above.
Z is particularly preferably phenyl which is unsubstituted or substituted by sulfo, methyl, methoxy or a reactive radical of the formula (2a) defined above, 2-naphthyl which is substituted by 1 to 3 sulfo groups, or a radical of the formula 
Z is especially preferably a radical of the formula 
in which R5 is hydrogen, methyl, methoxy or sulfo, (R5xe2x80x2)1-2 is 1 or 2 identical or different substituents chosen from the group consisting of methyl and methoxy and
Y is vinyl or xcex2-sulfatoethyl.
D is preferably the radical of a monoazo, disazo, anthraquinone, formazan, phthalocyanine or dioxazine chromophore, and particularly preferably the radical of a monoazo, disazo or formazan chromophore.
Examples of suitable chromophore radicals D are: 
in which (R6)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo and
Y is as defined above; 
in which (R6)0-3 is as defined above or is a radical of the formula xe2x80x94SO2xe2x80x94Y, in which Y is as defined and preferred above; 
in which (R6)0-3 is as defined above, 
in which Y is as defined above; 
in which (R7)0-4 is 0 to 4 identical or different substituents from the group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4alkyl, C1-C4alkoxy, amino, acetylamino, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo; 
in which R8 is C1-C4-alkanoyl or benzoyl, or in which xe2x80x94NHR8 is a fibre-reactive halotriazinyl radical of the formula (2e) defined above; 
in which (R9)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo; 
in which R10 and R12 independently of one another are hydrogen, C1-C4alkyl or phenyl and R11 is hydrogen, cyano, carbamoyl or sulfomethyl; 
in which (R13)0-2 is 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo; and
Y is as defined above; 
in which (R14)0-2 is 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo; and
Y is as defined above; 
in which (R6)0-3, (R7)0-3 and (R9)0-3 are each as defined above and (R6xe2x80x2)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy which is unsubstituted or substituted by hydroxyl, sulfato or C1-C2alkoxy, halogen, carboxyl and sulfo; 
in which (R6)0-3 and (R6xe2x80x2)0-3 are each as defined above; 
in which (R6)0-2 is 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo, one of the variables B1 and B2 is hydroxyl and the other is amino and
Y is as defined above; 
in which the benzene rings contain no further substituents or are further substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylsulfonyl, halogen or carboxyl; 
in which Pc is the radical of a metal phthalocyanine, in particular the radical of a copper or nickel phthalocyanine;
Wxe2x80x2 is xe2x80x94OH and/or xe2x80x94NR16R16xe2x80x2;
R16 and R16xe2x80x2 independently of one another are hydrogen or C1-C4alkyl which is unsubstituted or substituted by hydroxyl or sulfo;
R15 is hydrogen or C1-C4alkyl;
A is a phenylene radical which is unsubstituted or substituted by C1-C4alkyl, halogen, carboxyl or sulfo, or a C2-C6alkylene radical; and
k is 1 to 3;
in which Axe2x80x2 is a phenylene radical which is unsubstituted or substituted by C1-C4alkyl, halogen, carboxyl or sulfo, or a C2-C6alkylene radical, r, s, v and vxe2x80x2 independently of one another are each the number 0 or 1 and
Y is as defined above; and 
in which G is a phenylene radical which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl or sulfo, or a cyclohexylene, phenylenemethylene or C2-C6 akylene radical.
D is especially preferably a radical of the formula (5b), (5e), (5f), (5k), (5t), (5txe2x80x2) or (5v) defined above.
A particularly preferred embodiment of the present invention relates to compounds of the formula (1) in which D is a radical of the formula 
in which (R6)0-2 is 0 to 2 identical or different substituents from the group consisting of methyl, methoxy, sulfo, xe2x80x94SO2xe2x80x94CHxe2x95x90CH2 and xe2x80x94SO2xe2x80x94CH2CH2xe2x80x94OSO3H, in particular methyl, methoxy and sulfo; 
in which R10 and R12 independently of one another are each C1-C4alkyl and R11 is cyano, carbamoyl or sulfomethyl; 
in which (R7)0-2 is 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, acetylamino, ureido and sulfo; 
in which (R6)0-2 is 0 to 2 identical or different substituents from the group consisting of methyl, methoxy and sulfo, one of the variables B1 and B2 is hydroxyl and the other is amino and
Y is vinyl or xcex2-sulfatoethyl or 
The compounds of the formula (1) contain at least one, preferably at least two, and particularly preferably 2 to 8, sulfo groups, which are in each case either in the form of their free acid or, preferably, in the form of salts thereof. Salts are, for example, the alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine or mixtures thereof. Examples are sodium, lithium, potassium or ammonium salts, the salt of mono-, di- or triethanolamine or Na/Li or Na/Li/NH4 mixed salts.
A preferred embodiment of the present invention relates to compounds of the formula (1) defined above, in which
R is C1-C4alkyl;
R1 is hydrogen, methyl or ethyl;
X is fluorine or chlorine;
Z is phenyl which is substituted by one or more identical or different substituents from the group consisting of sulfo, C1-C4alkyl, C1-C4alkoxy and reactive radicals of the formulae (2a), (2b) or (2d) defined above; 1- or 2-naphthyl which is substituted by sulfo or a reactive radical of the formula (2a) defined above; a radical of the formula 
in which (R2)0-2 is 0 to 2 identical or different radicals R2 from the group consisting of sulfo; methyl, methoxy, xcex2-hydroxyethoxy, xcex2-sulfatoethoxy, xcex2-methoxyethoxy, acetylamino and ureido and (R3)0-3 is 0 to 3 identical or different radicals from the group consisting of sulfo, methyl and methoxy; or a radical of the formula 
in which Txe2x80x2 is independently as defined and preferred above for T, Xxe2x80x3 is independently as defined and preferred above for X and (R4)1-2 is 1 or 2 identical or different radicals R4 from the group consisting of methyl, methoxy, sulfo and reactive radicals of the formulae (2a), (2b) or (2d) defined above; and
D is a radical of the formula (5b), (5e), (5f), (5k), (5t), (5txe2x80x2) or (5v) defined above.
A particularly preferred embodiment of the present invention relates to compounds of the formula (1) defined above in which
R is methyl;
R1 is hydrogen;
X is fluorine or chlorine;
Z is phenyl which is unsubstituted or substituted by sulfo, methyl, methoxy or a reactive radical of the formula (2a) defined above, 2-naphthyl which is substituted by 1 to 3 sulfo groups, or a radical of the formula 
D is a radical of the formula 
in which (R6)0-2 is 0 to 2 identical or different substituents from the group consisting of methyl, methoxy, sulfo, xe2x80x94SO2xe2x80x94CHxe2x95x90CH2 and xe2x80x94SO2xe2x80x94CH2CH2xe2x80x94OSO3H, in particular methyl, methoxy and sulfo; 
in which R10 and R12 independently of one another are each C1-C4alkyl and R11 is cyano, carbamoyl or sulfomethyl; 
in which (R7)0-2 is 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, acetylamino, ureido and sulfo; 
in which (R6)0-2 is 0 to 2 identical or different substituents from the group consisting of methyl, methoxy and sulfo, one of the variables B1 and B2 is hydroxyl and the other is amino and
Y is vinyl or xcex2-sulfatoethyl; or 
The present invention furthermore relates to a process for the preparation of reactive dyes of the formula (1), which comprises reacting in each case about 1 molar equivalent of a compound of the formula 
in which
D, R, R1, X and Z are each as defined above, with one another in any sequence.
The diazotization of the compound of the formula (6) and coupling of the product with the compound of the formula (7) or a reaction product of the compounds of the formulae (7), (8) and, if appropriate, (9) are carried out in the customary manner, for example by diazotizing the compound of the formula (7) in mineral acid solution, for example hydrochloric acid solution, with a nitrite, for example sodium nitrite, at a low temperature, for example at 0 to 5xc2x0 C., and then coupling the diazotization product with the corresponding coupling component at a neutral to slightly acid pH, for example at pH 3 to 7, and preferably 5 to 6.5, and low temperatures, for example 0 to 30xc2x0 C.
The condensation reactions between the compounds of the formulae (7), (8) and (9) are in general carried out analogously to known processes, as a rule in aqueous solution at temperatures of, for example, 0 to 50xc2x0 C. and a pH of, for example, 4 to 10. If D is, for example, the radical of a monoazo or polyazo chromophore, instead of the compound of the formula (9), it is also possible to employ an intermediate, for example a diazo component or coupling component, in the process and to provide the radical D only in the subsequent course of the process by a corresponding diazotization and coupling reaction. The most important process variants are described in the examples.
The compounds of the formulae (6), (7), (8) and (9) are known or can be prepared analogously to known compounds. Any introduction of a carboxy- or carbamoylpyridinium radical X or Xxe2x80x2 is as a rule carried out after a condensation reaction of the corresponding cyanuric halides.
The dyes according to the invention are fibre-reactive. Fibre-reactive compounds are to be understood as meaning those which are capable of reacting with the hydroxyl groups of cellulose, the amino, carboxyl, hydroxyl or thio groups of wool and silk, or the amino and, where appropriate, the carboxyl groups of synthetic polyamides to form covalent chemical bonds.
The dyes according to the invention are suitable for dyeing and printing widely varying materials, such as fibre materials containing hydroxyl groups or containing nitrogen. Examples are silk, leather, wool, polyamide fibres and polyurethanes, and in particular all types of cellulosic fibre materials. Such cellulosic fibre materials are, for example, the natural cellulosic fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose. The dyes according to the invention are also suitable for dyeing or printing fibres, containing hydroxyl groups, which are contained in blend fabrics, for example mixtures of cotton with polyester fibres or polyamide fibres. The dye mixtures according to the invention and the dyes according to the invention are particularly suitable for dyeing or printing cellulosic fibre materials. They can also be used for dyeing or printing natural or synthetic polyamide fibre materials.
The dyes according to the invention can be applied to the fibre material and fixed to the fibre in various ways, in particular in the form of aqueous dye solutions and printing pastes. They are suitable both for the exhaust method and for dyeing by the pad-dyeing method, in which the goods are impregnated with aqueous dye solutions, which may contain salts, and the dyes are fixed after treatment with alkali or in the presence of alkali, if appropriate under the action of heat or by storage at room temperature for several hours. After the fixing, the dyeings or prints are rinsed thoroughly with cold and hot water, if appropriate with the addition of an agent which has a dispersing action and promotes diffusion of the non-fixed portions.
The dyes according to the invention are distinguished by a high reactivity, good fixing capacity and a very good build-up capacity. They can therefore be employed by the exhaust dyeing method at low dyeing temperatures, and require only short steaming times in the pad-steam method. The degrees of fixing are high and the non-fixed portions can easily be washed off, the difference between the degree of exhaustion and degree of fixing being remarkably low, i.e. the soaping loss is very low. The dyes according to the invention, and in particular the dye mixtures according to the invention, are also particularly suitable for printing, especially on cotton, but also for printing nitrogen-containing fibres, for example wool or silk, or blend fabrics which contain wool or silk.
The dyeings and prints produced with the dyes according to the invention have a high colour strength and a high fibre-dye bond stability both in the acid and in the alkaline range, and furthermore a good light fastness and very good wet fastness properties, such as fastnesses to washing, water, seawater, cross-dyeing and perspiration, as well as a good fastness to pleating, fastness to ironing and fastness to rubbing.
The following examples serve to illustrate the invention. The temperatures are stated in degrees Celcius, parts are parts by weight and percentage data relate to percentages by weight, unless stated otherwise. Parts by weight bear the same relation to parts by volume as the kilogram to the liter.